HUE034280T2 - Atz fused grains - Google Patents

Description

Teetinsral field 1% 'ïfty&amp;nüm reimen ΐ<> lesed grains bäSsil m ttíumíná, titpioro »side sndglrcbma árki to ts stsiesed product oomprpng such grain;;, such 3. sintered produeä Iking itwatdedso comedntp contact with s molten in a iah

Prior art la order to ix; able to ha rood in such an ágii«, a ceramic sintered product must have a pod: mámámí Stswopig a good psisMes to &amp;&amp;$*£; shookg and a good coolsten resistance its eotpet WÄ the mohon metal, The choirs ok the grams ttsed for oranulaeUtrlng the product is, to that end, a determining factor. Λ síidé gat« w to particular used itt the eoailnuons casting of sice; in order to open or close tundishes or discharge orifices of ladies Ϊ» fluid annomnk-ation with Ifspf molds, via a continuous casting rsoÄ or slidiitg noxtde,

Conventionally, the iihtSe gates are obtained by sintering a mixture of corundum and of fosod zirconia-muiiite grains and optionally {used aium|na-Ktsconi&amp; grains, UP i mo 7m describes: a slide gate manalwiured by sintering a mixture txartprising iused grains having hetweeti if% add 50% ofshtmina ΑΙ#?, bthwests Wé\-mà\40% of Ti02and more than Sb% of zirconia. as weight percentages, US 4 Mb 950 A describes continuons casthtg noxzies and discloses fused parttclcs based on alumina, titanium oxide and Peónia “ATZ” comprising 42-79.3 ws% aiutrtitta, 20-4(1 m% zirconia, 0,5-(6 wt% titartiuns oxide, and up tt> 2 wt% of Si02 ;Fe203 and Ha:iO (wt% denoting weight percentages). US 2008/203627 AI describes ceramic articles having good reihte tory and thermal shock resistance properties, obtained by sintering a eotnpdsiiiö« SOcb as 33.64 wt% Aigik; 42,19 wt% Tiö-g 24.17 wtv» ZrOj; 3 wt% ¥,(%, K.R 2003 0000081 A relates to moitett metals and describes ceramic products: that are resistant to corrosion and to thermal shocks, obtained by sintering (slum loom tiranaié attd olreonium m the presence of Mg£y An; example of the composition is> SO rnoibk A1¾ ΓΚ>$ and 50 mol% AfTîCdï to which 6 mol% are added; Le.: 25.25 wt% AU% 39.55 wt% TiO?; 30.44 wt% ZrO>; 4.76 With YA>w

There is a; constant: need for novei grams capable of being used in Afered products that are intended to; be in cohtaet with a molten metal, in pameniar in slide gates and that have tniproved mechanical properties: add also a good resistastee to thermal shocks, QSs objective of the ihvcntioir te to itiset Uns need.

Summary of the Invention

Aecprdmg to sise: invest;ion, this objective ;is MM&amp;éM by tobahs of a fused: pain comprising, idf a total of}00%· ~ Üfem 1054 preferably more ibtp 1534 and fess ®m #54 preferably fess titan 35% ofalutsina AbOg ·« more fedd 1053, preferably more than l S% äfet fess than 5054 er fess than 4554 m ífess $ίρ40?4 or fess ihau355y oititanirtst? bioffe T.H^ ~ moife than- 21%, preferably moi® than :1554 $8# fess than 50¾ and, preferably, fess than 4535 of zirconia (ZtOj 7-3¾¾% of feiffek - miyredhsn 154 preferably mope than {*.%> preferably «sore than 2¾. peferafeymore than 2.5% and loss ihan IW% fess than 9%, preferably less than S% of a compound selected feom ÉP gpup consisting of MgÖ, CaO, FeyD?, €r?0.;> Muffe. Lafeh, ïft GujOj anti mixtures thereof; - fess than 29% of silica $IO>:, - fess than 1054 preferably fess than: 554 fess É4U 954 or fess (ban 3% elfe eompofefe selected from the group consisting of the oxides of tbs elements: Sr. M&amp;. &amp; and Bs, and mixtures thereof; ~ fess than 25» of other oxide species; the pereeatages being percentages by weight on the basis of the oxides. Λ ftsed grain according m fee indention may also have one or more of the following features: ... T he weigh? eonlcot of MgO Is greater than 154 preferably greater than 1.5% and/or less than 9% and. preferably, less than 05¾.

The weight contera oi'Ce.0 is greater than 0.55b, or greater than 0.334 greater than 154 greater titan Î ,53¾. and/or less ihau 95», or less than §54 or less than 554 or less iitrm 394 - The weight contera of Ygfe is greater than 0,53b, or gresfer than 0.?%, greater than 1%, grenier than 1.55». and/or les;-, ibati 855, nr fess than 554 or less than 35¾. «* MgO, CaQ and Y;!0* are presem at the same tlmsr - Thecon?C!.i m iti'O MrO. - UO ·» tf m* ) w le», than ?%, or less dam 0.5%, ** The compounds belonging ro the group of oxides, nitrides, oxynitrides, carbides:, oXycafbides* earbtsnbr ides and metallic species of iron, vanadium and:chromium are impurities. ™ rite content td each of srdtl alkali mcml oxides artd/or alkaline-earth metai oxides Is fess fbp 99», or less titan 354 or less than 1%. - Ore compounds belonging So the group of oxides, nitrides, oxynitrides, carbides, oxycarbidcs, curhonitrkles and meudlie species of sodium ami other alkali metals are impurities. - The cornent of mUm k greafer $rn 0iB4 greater than 1%, grmm Mmi 334 and/or fe% than 1354 iessthan 1399, less than: 1235, less than 1P4 A: powder comprising, or even ennsfering bf ghbos according: to dm invention: and tbc tbc of wit a powder for thesmanafaeture of a slide gate Or of &amp; lining of a. feruace, for example as indyctfen furnace, m particnisribr melting métáiig Is described· Tib powder may is particular be of the dry ramming mix or “DYCfe dry vlbratabte mix on dry reffeettny, type. :$ϋφ (á^Mr^mitr than 2 μ»?,. g$g$?f t|ab I P»vöf .gtèâihrÉao i#':|ug er: greater tet Μψ$ and/or Jos-s than it unn, less than 'f Wm, less than 5 asm- hs®5 ihm 2 .mm, iast: thao.S m?«, to ism.kmm* or less man-500: por.

The invention also relates to a sintered product obtained by sintering a; powder according to *b,e mvemioo, in particular in the form of a Iming or a slide gate. iTefèfably, die wmMm hmm &amp;pmperm\ty of less thatrf ö%yft;«s 20%, or less than 15%. A process ft»· manufacturing a powder of fused grains according to the invention, comprising the following success ive si«?:·», is described a) ushdhg of raw materials So as to %rtp a fesdstbek, b) melting of said ieedstock antis TittöhgävmiÄai is obtained, c) sol id living said molten matériái, d> optionally, and in pániéul« if step ¢) does not result in grains being obtained, nnlling *3*° soi id moss so as: to obtain a powder of grains. the row snbterialg: are chosetrirs step: # so that the solid mass ..obtained at the end: of step C); has A composition in siecoidimee whir that of a grain accordmgto the invenoon. île «se of 3: slísieted potciiiCt aeeordsngdo :d;e mmKipn, m m aoplkadio» Is κΜΦΜ/β Mÿtcmâlü # thermal shock and or in which lids Incontadl: Wimdhtolfeo omíaíyio pftlcafar itt thé form of a liningor a slide gate,, is diso descrlhed. In-prie«!^ if installation eftoserdrom a bpnoce sod a slid® gate comprising a slofored product obtained by shnéríttg s powder of grains according to the itt vent ion, in particular in a region wbetwsaid sintered ptxidsel is intended to be in contact with a molten metal. tM'kdftoos ·· in the pmseoi description and claims, unless otherwise nteniioned. nil the petcentnges arc weight percentages. In particular, nli the eppsposiioás of : a gmitt arc given as weight percentages ott the basis of die oxides of the grain. • A “molten matemr is a liquid mass winch, in order to retain its shape, must be kept in a container, if may content a few solid particles, but in an insuffofem amount tor them to he able to structure said mass. - "Other oxide s-x?de?'' denotes all the oxide compounds that ate not mentioned elsewhere, fe, other than .Al,0:!, Ti€% ZfO.;, Hf(>;. MgO, CaO. FsjCh, CrdT, MnOj. La/h. Y\>C>,. GaA>,, SiD, and the alkali metal oxides and/or alkaline-sard: metal oxides. * Tbd term “impurities” is understood to unintentiohaliy lotrodueed with the raw materials or resulting from reactioos with these eowdituonts. The hnpttÄs are not necessary const latents huf merely constituents that are tolerated.

The tern “zirconia"' reim to zirconium oxide ZrO;: and tire traces: of liafniunt oxide BUT;, not chemically separable from ZrO;; ami always naturally present in sources of ZrOj. These traces of M£ö> represent lm than 2% of the «eight of the »«s^oula, llssisriam oxide is ag^er^önst^á to be us? Impurity, nor so b« :aiS %Shgf oxide species''. ... fhc pression "median diameter' oí a powder of grains, generally denoted by d«, mfets to the divides %pS tdfslsfe powder Mè :fini mâ. seeemtf: pispiabeos: thai ®ν·;*φ§. Μ volume, these fim and s^ond poptfiatiop. cö8pft#»8fyBmias?ÄÄve a dtmswter greater îhats, ot respeUiveSy feu than, the m$W diameifr.'Äs mpm&amp;ím itat o£»ê m*" h «nüerstood. U! mean the dimeter of sise sphere oRk same volume. The diats-cter of she grain··: of a powder is: conventional evaluate by a cisaiairtaniodion of tbe par*ick: size distribution ca«tod oat wish a laser panicle size analyzer. Tlx· laser panlde size analyzer way be. for example, a Panina the company BORIBA. - fha terns "grain" refers to a pari irk; Paving a diameter of less than H) mss.

Detailed desortpiion

Use description that purposes smd dtses not iimitshe, invenfioh.

Fused grttins according lb tbs myesttsou ?My be nnmuiactured according So ihc afereissentioned: steps a) to d). fn step à% -vm. snuieriafe: am; dodÂto^üÿ imeasured mt m as M obfoih dise desired eomposidpti, then nsixed m order to form the feedstock.

Tiiatsitssp jssíiv be liittsidiseed: in un y toms, istpattiMkr mdk íoíss ïd an oasde 11(¾ or in sïsemilî&amp;iist'iss. :0( : in the Toros of n zimoniss-Sitamuns oxide alloy, or of alumina tiunsate, 1« one embödissséoí, (ho alkali mein! oxides sod aiteiiino-eadh metii ssxSdoa are impurities. it is considered that a consent of fetber Oxide speies” of less ih;ns 2% does not suppress ihe ieehoical effect provided by the invention. The ‘hasher oxide species“ may also be impurities.

Preferably, the content of impartîtes is less than 3%. less -hart 2%, less than s%. or less than 0.5%, ín step .0¾ use is preferably made of an electric arc fiapttéèt bötsÄadvwt fornaces: css- he envisaged, such as an induct em furnace or a plaona farnace, provided thaï they make it possible· to completely tneit the feedstöók. The firing is preferably canned out under höattá! cohditions, forexanspte under argon, or öxtdizthg conditions. preferably at as mospheric pressure. iss step «)., the coolingassay k rapid, i.e. so shat §e moke« rnmmi is completely solidikd io iess than d sbmssses. For example, it may result from a casting info CS molds as siescrikil its lil||yPI,li't:t::'för tett^tgpítbhipifitmáyraistr-kdlow (ingot cooled In site open air or anbepa| biocki.

If step e) does riot snake iS ipösstble to ouvaiss s iposyder^öígrisini!,. öf if theilc grains do nos have a ^usable pâSrtîëiOsslzOïfor théantended appSicatsou, miiiiug ptap: d)1 Rtay hecsrdeifotst, accofxiing to convcpribn&amp;i techniques.

The nsasrnfitemiy Ot a sintered proüt set according to the dnooskfossp-few· a powder pf'gfoifis abcordiisg :fo the mvemiots. tasny be canned mu fo any known process.

ExstmpU®

the wav of iihssmdioo and do not IMI fesii thé ekwoples. She stopples were prspat'ái te®.M Mowing: raw nisteHtdsi ** mstem enmprismg mom te« 9$% offJO^. pld fey the compápy Altltfegm: dr stele comprising more than 95« <s of ΠΟ ; and having a media«' dfernetet 4m of »wund 120 wm,-p|| fey &amp;e «««papy E«fop M metes, - alumine ARM comprising more than 9S% of AU'.fe soil by the company Álca« ami h&amp;vfeg a median diameter % of Afentsd SS ppi, - silica SiO; Ä a degree of parity of greater than 99.5% sod having m pSiiiatt diameter d5<; of 208 pro, sold by the company Sbraco, ~ magnesia Mgí) wife ffdegtee:Ofpurity of greaterfean 9t%, ntoiedfeslffeteh of fee particles haying a diameter between 0.25 sod:ï » sold by die eompsmytedniag;, ~ fet'emna with s degree of pnrlly oijgreafer than $t<5°4 add. h$M$ "I .podM idlistmetsr d^olO $ ·ρ%-sold tmder the reference CC10 by the company baint-Oofealo .lirPro. 1¾¾ raw matetifes mere measured 'put. -má; mim&amp;i In ofefer -to ffeftn M teedteck of appropriate composition. for the nmmtiaetare of the sample of example: 3, the feedstock was pressed itf orpr tp tern a prefer® &amp; the: Ibrtn of s disk haveng a diameter ofl 3 dim and a height of 13 mm. fór i|io nisoofeemre ofIte samples ofexamplex I.» 2 and 4, the feedstock sva;; nsefted ifepbifebds am isrnaec., In ali, «öder oxidizing electrical conditions, festi cooled. The solid masses: obtained wer® ötmi miiied and screened In: order to obtain powders having a median diameter <d>fe between 10 and i5 pm

The ...powders· offered: gifem were pressed ip orderte ibrni preforms in the form of disks, similar to that of example 3.

All of the disks were then sinferedfe nteniperafereof IdaCfC for 4 hoursv The samples of examples 1 M 4 were fens obtained.

The samples prepared wefefesn analyzed, Tlmressfes arefissembfed In tafele I.

The: chcmlcai composition, irullcawd as weight percentages on the basis of fee oxides, was determined: by X-my fluorescence

The porosity fPj was determine;! emwentfenaily by messmfeg: the ;gdMeÄ' tfeagiy· W$i -dfeseÄ density determined, on the Milled samplerfey 'fesifent pyenometry.

The expanses® coefficient ";f' was measured between S(P€ und tSOö ’C.

The eompressixe strength •'b'" was determined at ambient temperatare, in a conventional manner, ion; samples I to 4.

Table I

*; comp&amp;tanve «»ample :! fttôicateS'thar the grams according to Síié iovéíltlön {example átfésüli; m.&amp;. sintered productMm has a particularly high mechanical strength.

The :cfpt|>a$ssm of example ..$ pgiifexampie '3 shows; The tidvasuage of grains öbiíóoed: by melbpg. ípferréd so as bíuseá” gramsylIMs is because the melting ; of the ièedstock iPSiÉa in a tmtlsr mechanical strenphand a lowef porosipjíssalíiiig St possible So ISmifthe ei8nmf0n/mjä^ÄS:ihiteitö«;

Tibié T shöwxíbafThepisos aecordUigj» .inventionlower than: thai of example 4* or than thaï of fused muiiite-slA:oma grains (of the order of 7*Wie>C‘') mibm that: effused aiutninamirconkt gmins (of the otder of ÍÖ - lO^C"). This makes it possible M obiaia paduets havlag/äbeifer resisfasee so thermal shocks, 'Tli^::«^Äl|in«-gte«S:;P^s^ «η the sample of example 2 wifp æhâfâotefized by IX-ray diffVsetlmu A main phase Is observed consisting ol an oxide phase in Solid; solution, of psimdoAuookhe type, comprising thanking aluminum, magnésium tod Prcomum M propoAioos such that the pSehdo^hropkiie type: phase cormspoods solÄotlally ip she idmusMion ÍAI-íTsÖsMIHx'T i;A)*P%TiZr(%}« with ο. î < s < 1 and 0 < y < 0.9 arid κ - i->;-y. Also observed is a silicate phase mid another phase essentially consisting of titanium oxide and xkconia.

Furthermore, the stability of the crystalline phases present was verified by a rest consisting in fitopparfngs % Ismy dÄcfi^S«:^ÄÖ?ö«;päS0^ initially present; in; the saotpis of exasfipie: 2 to those prescrit in this same satdgfe sfea host iröätmepf of XÖÖ bötirs atkOÖAl

As is now clearly apparent the Invention provides a grain suitable tA being eheeuveiy used in it with a molten meiah

Clf course* the invention: ft nçïi íísmtcd: to the embodiments of the examples, piyjyidpd ifof Ifkrtlmfivs purposes,

Claims (4)

superfine ATZ samnessi PATHFUL I HAVE YOUR PONS 1. Of v &amp; stot granules, smelyrusk. g'completed chemical composition vsn total KK)% 4> ani: more than 1θ% and less, stint 58% aluminum ancestors ALG:; - more, mini 1055 and less, sunt 58% iMnMIoxtd TICA more, mini 21% and less, sunt 58% zirconium (ZsOo ayemstkbán% <> oh - more, nets 1%% less than 10%, chemicals that are MeCM, Cn (MFed.l; ···. Crjöj, MsCK, Uy% Ht.) Include Yjöyi, 0% est and few of them selected from the group, less 28% silicktm'dioxkl SséA steeper, mini 10 % of these compounds are selected from the group consisting of oxalic oxides of alkali metal, selected from the group consisting of oxc and blend of earth, less melt% of oxide,% and percent by weight, based on the weight of the ancient times. A molten particle according to claim 1, comprising: - a plurality of ski intakes of $ 1 · ssysium oxide Ali; and / or desire more than 1% by weight of Titho:; and / or - a plurality of sines of 25% Ci-oxy-d; more than 5% of a mixture of IV, CaCl 2, Fe 3 O 5, P 1 MsOrA Ltoö, YjOrk Gi% QH, and mixtures thereof, selected from the group consisting of powder; and A is less than 5% of a compound having Sr, Na, K.4 and iBad, some of which are selected from the group; where the percentages are total, based on the weight of the oxiclock, A mesh of melters according to any of the preceding claims, comprising:; Less than 35% Aloe Vera Oxygen AlsOg and / or less than $ 4% Ryano Dioxide! TiGg and / or less than 45% zircon exldot; and / or less., such as 9% such a mixture, Mgö, CaO, Pe; (α3-k'mOs, Μη € Μ> La:; 33, YyÖsA, pound, and and / or less or 4% of a mixture of $ M, Na, Ki, and Ba, valastin mixtures of these are: iron ore, iron, select; tbsoegxzázaíékok, 4. M previous Claims ssstrmt] melted set containing less than 40% titanium walnut time TiOg and / or ya V less, mini: 3% component, snteiy of Sr, Ne, K and ßa osklja.U, and eaten contain a mixture selected from the group; where the percentages are the centuries-old centuries of mass, or m! a melted granule according to any of the y-points, wherein the MgO content of the bellows is greater than 1.5% and less than%%, where the percentage is the percentage by weight of the ancient times. £ 4¾ elbgO claims for which the melted wax is used, where the CaO is greater than l, S% and less, in sieve mass, siM, ÍS, alphabet &amp;amp; , where Y> Ck content is higher in mass, spin} .S% and stiffer, which is 8%. altot percent percent of oxkksk mass projection percent. melted according to the pay slip of the previous one, where {Cr? CK ·; - MnOj4 l..a,> 0 ;; * h tla-Oj) content less, sttirt 5%,% by weight of ancient times. 4¾ | lèîtb · 3i® $ ypdtWö | .You have melted clay chips, where each alkaline fess is steamed: M &amp;amp; : 4%; oxides iispeggiequestion, credible, tyz: aibzb according to the demanding part of the shredded grain, aboi the alkali ösvd ésva§y: I am firing i (k 'ijsliiok tariaima less, tnísn t% of the oxidants mass percentage vetiive. ^ the need for a bala'mdyske senmi melted grain, ab «! &Amp; fæitciom oxfá .malom nstgyobb, tnint t * o. In the ancient times of pseudo-hunting, according to the claim of the prior art, wherein the content of xdiie di-oxide is higher, nnnt; V is". I j The following is what you read! grains. where the samsith-oxsci bored less, ssstst 15%, m oxid nyltin gusts! expressed. : 4th Ôo-nnn reading &nbsp; s n nn nn nn nn Ô Ô Ô sai sai sai sai sai sai sai sai sai sai sai sai sai sai sai iak iak iak nagyobb nagyobb nagyobb ks ks ks ks ks ks ks ks ks ks ks vos vos vos vos vos vos vos vos vos fok fok ogs ogs ogs ogs ogs ék ék ék ? he has an animal.